Composition for reducing readiness with which synthetic fibers accept an electric charge



United States Patent Office 3,211,646 Patented Oct. 12, 1965 It has been found that the readiness with which a wide variety of synthetic fibers accept an electric charge, which fibers therefore would develop a strong electrostatic charge when rubbed, can be substantially reduced with the aid of preparations consisting of (a) salts derived on one hand from organic monocarboxylic acids and on the other hand from bases of the formula in which R stands for a linear aliphatic hydrocarbon radical with 11 to 17 carbon atoms, R and R each stands for an alkyl radical with 1 or 2 carbon atoms and m=l or 2; (b) bases of the formula R'CHN-CH (CHZ) N g R4 in which R stands for a linear aliphatic hydrocarbon radical with 11 to 17 carbon atoms and at least one double bond, R and R each stands for an alkyl radical with 1 or 2 carbon atoms and m=1 or 2; used in the ratio of base to salt of 1:10 to 20:10; and (c) a mineral oil.

These preparations are particularly suitable for treating hydrophobic fibers, for example semisynthetic fibers from cellulose esters such as cellulose diacetate or cellulose triacetate, from polyesters such as polyterephthalic acid glycol ester, from polyamides, polyurethanes or polyacrylonitrile. Likewise suitable are fibers from copolymers or from mixtures of the afore-mentioned polycondensates or polymers, or fiber blends consisting of different synthetic fibers, if desired also mixtures of synthetic and natural fibers of animal or vegetable origin.

The preparations of the invention contain on one hand the salts of the composition defined above under (a) and on the other hand the bases of the Formula 2 mentioned under (b). The salts themselves are composed of organic monocarboxylic acids and of bases of the Formula 1. These bases are as such known; they contain an ethylenediamine (CH CH or preferably a propylenediamine radical (-CH CH CH and as the linear aliphatic hydrocarbon radical R with 11 to 17 carbon atoms, for example, a radical of one of the formulae 12,

or H C(CH or preferably a radical with a double bond such as the radical of the formula H3C(CH2)7CH=CH(CH2)7-. The radicals RCO need not be uniform, and the diamines may very Well be acylated with different saturated and/ or unsaturated fatty acid radicals. Thus, the acyl radical RCO may be, inter alia, the radical of the so-called commercial stearic acid, a product consisting predominantly of stearic acid and containing further higher fatty acids, more especially palmitic acid and a small proportion of oleic acid and having a mean molecular weight of about 270. Incidentally, with saturated radicals R it is of advantage to the solubility of these products to add a certain proportion of these compounds in which radical R is unsaturated.

The radicals R and R present in the compounds of the Formula 1 are alkyls with 1 to 2 carbon atoms, that is to say methyl or ethyl groups. R and R may be identical or different from each other.

As acids for the manufacture of the salts referred to under (a) there are suitable, for example, aliphatic monocarboxylic acids with up to 5 carbon atoms, such as propionic acid, or more especially acetic or formic acid.

Particularly good results in the use as monocarboxylic acids have been obtained with the quaternary compounds of the formula in which R stands for a linear aliphatic hydrocarbon radical with 11 to 17 carbon atoms, R and R each represent an alkyl radical with 1 or 2 carbon atoms, X stands for a halogen atom and m=l or 2. Thus, these quaternary ammonium compounds are derived from bases of the Formula 1 and from halogenacetic acid and may also be prepared in known manner from the afore-mentioned starting materials by quaternating tertiary amines of the Formula 1 with halogencarboxylic acids of the formula (4) XCH fCOOI-I in which X has the above meaning. In this case, too, the alkyl radicals R and R contain 1 or 2 carbon atoms so that the quaternary compounds contain a radical of the formula X CH:COOH

in which p and q each is 1 or 2.

The bases of the Formula 2, to be added to the salts from monocarboxylic acids and bases of the Formula 1, must contain as the linear aliphatic hydrocarbon radical R a radical with at least one double bond, and also in this case the residue of the composition (that is the radical of oleic acid) is preferred.

When the base of the Formula 1 from which the salt is derived and the base of the Formula 2 and/ or the base of the quaternary compound of the Formula 3 which may optionally be used as monocarboxylic acid are identical, the manufacture of the mixtures may be simplified in certain respects. Thus, for example, instead of separately manufacturing the quaternary ammonium compound of the Formula 3 from 1 molecular proportion of the compound of the Formula 1 and 1 molecular proportion of halogencarboxylic acid and then preparing the salt with a further molecular proportion of the base of the Formula 1, 2 molecular proportions of the base of the Formula 1 may simply be reacted with 1 molecular proportion of halogencarboxylic acid to give rise to 1 molecular proportion of the salt of the composition defined under (a) above. If the base contains an unsaturated radical R it is even possible to react an amount of the base in excess of 2 molecular proportions with 1 molecular proportion of halogencarboxylic acid to form directly a mixture, suitable for making the preparations, of 1 molecular proportion of salt and the excess of the base that has not been consumed in the quaternation and neutralization.

Irrespective of whether the last-mentioned procedure is adopted or the ingredients are finally mixed together, it must be ensured in any case that the ratio mentioned above is maintained, that is to say that the mixture contains for every parts of the salt of the composition defined above under (a) at least 1 part and at most 20 parts of free base of the Formula 2.

By suitably varyingthe proportions of the ingredients it is easy to prepare mixtures that are readily soluble in mineral oils and these solutions 'lend themselves well to emulsification in water. The mineral oil solutions preferably contain from to 30% of the salt-base-mixture and from 85 to 70% of mineral oil; These properties have a specialsignificance for the following reasons:

As is know, a so-called antistatic agent, that is to say a substance capable of reducing the electrostatic charge, is used in processing synthetic fibers since electrically charged fibers tend to stick, for example to machine parts, or to repel one another in spinning. Furthermore, the fibers must be rendered soft and capable of sliding easily to ensure that the final yarn is pliable, and easy to spin and weave. The lubricating and softening agent used for this purpose is very frequently a mineral oil. Since the mixtures of the kind defined above are readily soluble in mineral oils, it is easy to achieve with such solutions readily and advantageously both effects simultaneously, namely a reduction of the electrostatic charge and the softening and lubricating. By the addition of the new mixtures the viscosity of the mineral oils, which is of importance to their suitabilityas lubricants, is at most affected to a minor and wholly acceptable degree. The preparations can therefore be applied to the fibers in the usual manner, exactly as is practized with mineral oil alone. By virtue of the readiness with which the mineral oils can be emulsified with the mixtures of the invention consisting of salts and bases, the mineral oil is easy to remove the final product by rinsing with water.

Unless otherwise indicated, parts and percentages in the following examples are by weight.

Example 1 36.5 parts of oleic acid dimethylaminopropylamide of (1 mol) are, mixed with 6 parts of acetic acid (1 mol) while being cooled. The resulting acetate is liquid and readily soluble in water.

9 parts'of the above acetate are mixed with 1 part of oleic acid dimethylaminopropylamide. 1 part each of the resulting preparation is dissolved in 4 parts of the mineral oils marketed under the trade names Mentor 28 and Vaselineoil 250T? (Esso). The resulting clear solutions have a viscosity which hardly differs from that of the mineral oils. When these mineral oil preparations are poured into water, they form fine emulsions.

By means of a Godet preparation roller 1.5 to 2% of this mineral oil preparation can be applied to a polyamide thread which, after this treatment, displays good antistatic properties.

Instead of threads from polyamides there may be used threads from cellulose acetate or polyesters or filaments from polyacrylonitrile to which similar, good antistatic properties are thus imparted.

Similar results are obtained when the acetate is replaced by the formate or propionate of oleic acid dimethylaminopropylamide.

Example 2 73 parts of oleic acid' dimethylaminopropylamide (2 mols) are heated to 55 to 60 C. in a reaction vessel equipped with an agitator. In the course of 30 minutes 9.4 parts of chloracetic acid (1 mol) are added, the air is then displaced by nitrogen and the mixture is heated on for 4 hours a1: 55 to 60 C. The resulting tough paste gives in water a clear solution of neutral reaction.

A mixture of 4 parts of the resulting product and 7 parts of oleic acid dimethylaminopropylamide is produced with heating, whereupon a clear, slightly viscous solution forms.

1 part of the above mixture is dissolved in 4 parts of mineral oil, such as Mentor 28 or Vaseline oil 250T, whereupon a completely clear solution without appreciably increasing the viscosity of the mineral oil. When this solution is poured into water, good emulsions are formed. Threads or filaments from polyamide, cellulose acetate, polyesters or polyacrylonitrile can be rendered antistatic with these mineral oil preparations by the method described in Example 1.

Very similar results are obtained when the reaction product from chloracetic acid described in the first paragraph of this example is replaced by the reaction product from 2 mols of oleic acid dimethylaminopropylamide and 1 mol of bromacetic acid, made up into a preparation in the manner shown above.

Example 3 71.8 parts (1 mol) of commercial stearic acid dimethylaminopropylamide of the formula RCHN-OHz-CH2CH:N

(in which R" represents predominantly the radical H 0 are neutralized at 60 C. with 12 g. of glacial acetic acid (1 mol). The resulting acetate is solid at room temperature and is readily soluble in Water. 2 parts of the acetate are dissolved with heating in *3 parts of oleic acid dimethylaminopropylamide. After cooling, a soft paste is obtained which is dissolved as described in Example 1 in mineral oil, for example in Mentor 28 or Vaseline oil 250T to yield a preparation having a similar antistatic action.

Example 4 91.2 parts of lauric acid dimethylaminopropylamide (2 mols) are heated to 55 to 60 C. in a reaction vessel equipped with an agitator. In the course of 30 minutes 14.1 parts of chloracetic acid (1 mol) are added, the air is displaced with nitrogen and the batch is heated on for 4 hours at 55 to 60 C., whereupon a tough paste is obtained. The preparation gives a clear solution in water and the solution is of neutral reaction. 3 parts of this mixture are mixed with heating with 4 parts of the acetate of oleic acid dimethylaminopropylamide (see Example 1) and 3 parts of oleic acid dimethylaminopropylamide, and the resulting mixture is dissolved as described in Example 1. A clear solution is obtained, without the viscosity of the oil being appreciably increased. 7 When the solution is poured into water, a fine emulsion results.

Insofar as its antistatic action is concerned such a mineral oil preparation closely resembles that which has been described in Examples 1 and 2.

Example 5 (1 mol) are mixed with 6 parts of glacial acetic acid (1 mol) and 9 parts of the acetate so obtained are mixed with 1 part of the oleic acid diethylaminoethylamide. 1 part of the resulting mixture is dissolved in 4 parts. of mineral oil, for example Mentor 2.8. The preparation is in the form of a clear solution of low viscosity and immediately forms an emulsion when poured into water.- Threads or filaments treated with this preparation 1305-- sess an antistatic finish.

in which R represents a linear aliphatic hydrocarbon radical containing 11 to 17 carbon atoms, R and R each represents an alkyl radical containing at most 2 carbon atoms and m is a whole number of at the most 2; (b) a base of the formula in which R' represents a linear aliphatic hydrocarbon radical containing 11 to 17 carbon atoms and at least one double bond, R and R each represents an alkyl radical containing at most 2 carbon atoms and m is a whole number of at the most 2; the ratio of base (b) to salt (a) being at least 1:10 and at most 20:10; and (c) a mineral oil which is present in an amount of 70 to 85 percent, calculated on the total of the ingredients )+(c)- 2. A composition for reducing the readiness with which synthetic fibers accept an electrostatic charge, consisting essentially of (a) an aliphatic monocarboxylic acid salt of an aliphatic monocarboxylic acid containing up to 5 carbon atoms and of a base of the formula in which R represents a linear aliphatic hydrocarbon radical containing 11 to 17 carbon atoms, R and R each represents an alkyl radical containing at most 2 carbon atoms and m is a whole number of at the most 2; (b) abase of the formula Ra R-CHN-CH2(CH2)m N in which R represents a linear aliphatic hydrocarbon radical containing 11 to 17 carbon atoms and at least one double bond, R and R each represent an alkyl radical containing at most 2 carbon atoms and m" is a whole number of at the most 2; the ratio of base (b) to salt (a) being at least 1:10 and at most 20:10; and (c) a mineral oil which is present in an amount of 70 to 85 percent, calculated on the total of the ingredients 3. A composition for reducing the readiness with which synthetic fibers accept an electrostatic charge, consisting essentially of (a) a monocarboxylic acid salt of (1) a monocarboxylic acid of the formula in which R represents a linear aliphatic hydrocarbon radical containing 11 to 17 carbon atoms, R and R each represent an alkyl radical containing at most 2 carbon atoms, X represents a halogen atom and m is a whole number of at the most 2, and of (2) a base of the formula in which R represents a linear aliphatic hydrocarbon radical containing 11 to 17 carbon atoms, R and R each 6 represents an alkyl radical containing at most 2 carbon atoms and m is a whole number of at the most 2; (b) a base of the formula in which R represents a linear aliphatic hydrocarbon radical containing 11 to 17 carbon atoms and at least one double bond, R and R each represents an alkyl radical containing at most 2 carbon atoms and m' is a whole number of at the most 2; the ratio of base (b) to salt (a) being at least 1:10 and at most 20:10; and (c) a mineral oil which is present in an amount of 70 to percent, calculated on the total of the ingredients 4. A composition for reducing the readiness with which synthetic fibers accept an electrostatic charge, consisting essentially of (a) a monocarboxylic acid salt of an aliphatic monocarboxylic acid containing up to 5 carbon atoms and of a base of the formula in which R represents a linear aliphatic hydrocarbon radical containing 11 to 17 carbon atoms, R and R each represents an alkyl radical containing at most 2 carbon atoms and m is a whole number of at the most 2; (b) a base of the formula in which R and R each represents an alkyl radical containing at most 2 carbon atoms and m is a whole number of at most 2; the ratio of base (b) to salt (a) being at least 1:10 and at most 20:10; and (c) a mineral oil which is present in an amount of 70 to 85 perecent, calculated on the total of the ingredients (a)+(b)+(c).

5. A composition for reducing the readiness with which synthetic fibers accept an electrostatic charge, consisting essentially of (a) a monocarboxylic acid salt of (l) a monocarboxylic acid of the formula in which R represents a linear aliphatic hydrocarbon radical containing 11 to 17 carbon atoms, R and R each represents an alkyl radical containing at most 2 carbon atoms, X represents a halogen atom and m is a whole number of at the most 2, and of (2) a base of the formula R1 R-fi-HNCHz(CH2)mN 0 R in which R represents a linear aliphatic hydrocarbon radical containing 11 to 17 carbon atoms, R and R each represents an alkyl radical containing at most 2 carbon atoms and m is a whole number of at the most 2; (b) a base of the formula HaC-(CH2)7-CH=CH(CHz)7(fiNHCHz(CHz)w-N in which R; and R each represents an alkyl radical containing at most 2 carbon atoms and m is a whole number of at most 2; the ratio of base (b) to salt (a) being at least 1:10 and at most 20:10; and (c) a mineral oil which is present in an amount of 70 to 85 percent,

calculated on the total of the ingredients (a) +(b)+(c). 6. A composition for reducing the readiness with 7 which synthetic fibers accept an electrostatic charge, consisting essentially of (a) the acetate of the base of the formula CH3 CH3 CHz-CH OH -N o1 CHI-c o 011 and of the base of the formula 9 I 7 CH3 H O-(CH -0H:CH-(OHzh-fi-HN-OEh-CHrOHz-N (b) the base of the formula given under (a); the ratio of base (b) to salt (a) being at least 1:10 and at most 20:10; and (c) a mineral oil which is present in an amount of 70 to 85 percent, calculated on the total of the ingredients (a)+(b)+(c).

8. A composition for reducing the readiness with which synthetic fibers accept an electrostatic charge, consisting 8 essentially of (a) the acetate of the base of the formula Hac-(OH2) fiHN0H,oHr-0H,N

I CH3 (b) the base of the formula CH; H C(OH2)1GH=GH-(CH -fiGH OH,cH,N

the ratio of base (b) to salt (a) being at least 1:10 and at most 20:10; and (c) a mineral oil which is present in an amount of to percent, calculated on the total of the ingredients (a) (b) (c) 9. A composition for reducing the readiness with which synthetic fibers accept an electrostatic charge, consisting essentially of (a) the acetate of the base of the formula 0 m HaC(CH2)7CH=CH(CHz)7-fiHNCH2-CH2N O CzH5 (b) the base of the formula given under (a); the ratio of base (b) to salt (a) being at least 1:10 and at most 20:10; and (c) a mineral oil which is present in an amount of 70 to 85 percent, calculated on the total of the ingredients (a)+(b)-|-(c).

References Cited by the Examiner UNITED STATES PATENTS 2,589,674 3/52 Cook et al 260--404.5 2,626,876 1/53 Carnes 2528.8 XR 2,717,842 9/55 Vitalis 2528.8 XR 2,730,464 1/56 Winsor 2528.8 XR 2,877,178 3/59 Bergman et a1 2528.8 2,956,949 10/60 White et a1. 2528.8

JULIUS GREENWALD, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3,211,646 October 12, 1965 Alfred Berger It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 5, lines 15 to 18, the formula should appear as shown below instead of as in the patent:

column 7, lines 20 to 25, the formula should appear as shown below instead of as in the patent:

Signed and sealed this 7th day of June 1966,

(SEAL) Attest:

EDWARD J. BRENNER ERNEST W. SWIDER Commissioner of Patents Attesting Officer 

1. A COMPOSITION FOR REDUCING THE READINESS WITH WHICH SYNTHETIC FIBERS ACCEPT AN ELECTROSTATIC CHARGE, CONSISTING ESSENTIALLY OF (A) A MONOCARBOXYLIC ACID SALT OF A BASE OF THE FORMULA 